CN1239983A - Refrigeration oil and working fluid composition for refrigerating machine - Google Patents

Refrigeration oil and working fluid composition for refrigerating machine Download PDF

Info

Publication number
CN1239983A
CN1239983A CN97180544A CN97180544A CN1239983A CN 1239983 A CN1239983 A CN 1239983A CN 97180544 A CN97180544 A CN 97180544A CN 97180544 A CN97180544 A CN 97180544A CN 1239983 A CN1239983 A CN 1239983A
Authority
CN
China
Prior art keywords
carbon atom
oil
acid
refrigeration
refrigeration oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN97180544A
Other languages
Chinese (zh)
Inventor
大岛良晓
荻原敏也
冨樫博靖
小林勇一郎
平幸治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Publication of CN1239983A publication Critical patent/CN1239983A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/24—Only one single fluoro component present
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/304—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
    • C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/32—Wires, ropes or cables lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/34—Lubricating-sealants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/36—Release agents or mold release agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/38—Conveyors or chain belts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/40—Generators or electric motors in oil or gas winning field
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/42—Flashing oils or marking oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/44—Super vacuum or supercritical use
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/50—Medical uses

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Lubricants (AREA)

Abstract

A refrigeration oil having a volume resistivity at 25 DEG C of not less than 1 x 10<13> OMEGA .cm, including (a) an ester base oil, and (b) a compound represented by the formula (1): R<1>O(EO)m(PO)nR<2>. In said formula, R<1> is a hydrocarbon group having 1 to 36 carbon atoms; R<2> is hydrogen atom, a hydrocarbon group having 1 to 36 carbon atoms, or an acyl group having 1 to 24 carbon atoms; EO is oxyethylene group; PO is oxypropylene group; and m is a number of from 0 to 50, and n is a number of from 0 to 50, with proviso that the sum of m and n is from 1 to 100. In the refrigeration oil, the amount of (b) is 2 to 25 parts by weight, based on 100 parts by weight of (a). A working fluid composition for refrigerating machine including the above refrigeration oil and one or more hydrofluorocarbons.

Description

Refrigeration oil and the working fluid composition that is used for refrigerating machine
Technical field
The present invention relates to contain the refrigeration oil of ester group oil and special ether compound and be used for the working fluid composition of the oily and hydrogen fluorohydrocarbon of above-mentioned refrigeration of containing of refrigerating machine.
Background technology
In recent years, in order to protect ozonosphere, will be forbidden by law or control as the refrigeration agent chlorine hydrofluoric ether (CFC) and the Hydrochlorofluorocarbons (HCFC) of refrigerating machine and motorcar air conditioner at present.Therefore, hydrogen fluorohydrocarbon (HFC) has been used as the hydrofluoric ether surrogate.Because the hydrofluoric ether surrogate has higher polarity than CFC or HCFC, therefore, they and lubricating oil for example have relatively poor compatible ability as the mineral oil and the alkylbenzene of refrigeration oil usually, therefore cause two to be separated at low temperatures., compare with mineral oil or alkylbenzene in recent years for this reason, more commonly use those materials with high polarity, for example ester, ether, carbonic ether etc. are as refrigeration oil.
Yet above-mentioned therein refrigeration oil more is applicable under the situation of hydrofluoric ether surrogate refrigeration agent, because the viscous substance in the refrigeration cycle has produced the problem that refrigerating efficiency descends, this problem is impossible in routine refrigeration oil.Viscous substance in refrigeration cycle may be because the products of metamorphism of the refrigeration oil of heating, air and water generates in refrigeration cycle and the various oil that use in the production of refrigerating machine etc. and assembling process, comprise mineral oil and hydrocarbon synthetic oil, the oil of for example drawing, cutting liquid, cosmoline, press oil and cleaning liquor.
Consider the mixing oil of ester group oil and polyalkylene glycol by accident, reported special polyalkylene glycol of mixing and hydrofluoric ether surrogate and had good consistency (the open 5-32985 of Japanese Patent), or used polyalkylene glycol as viscosity modifier (the open 5-209181 of Japanese Patent).Yet, be not reported in so far and use polyalkylene glycol in the refrigeration oil of the present invention to suppress the formation of viscous substance.
On the other hand, the open 8-73880 of Japanese Patent discloses a kind of refrigeration oil, and its Han You oxazoline compound is to suppress the formation of viscous substance.Ran Er ， oxazoline compound itself has poor thermostability, therefore because it makes the have greatly increased tendency of viscous substance of refrigeration oil deterioration.
The purpose of this invention is to provide the good viscous substance that has that is used for hydrofluoric ether refrigeration agent surrogate and form inhibiting refrigeration oil.
Another object of the present invention provides the working fluid composition that is used for above-mentioned refrigeration oil of containing of refrigerating machine.
Another object of the present invention provides uses refrigeration oil of the present invention to suppress the method that viscous substance forms in refrigeration cycle.
Another object of the present invention provides and suppress the reagent that viscous substance forms in refrigeration cycle.
By following description these and other objects of the present invention will be tangible.
Disclosure of the Invention
By the conscientiously research to the problems referred to above, the inventor has found to contain the refrigeration oil of ester group oil and special ether compound, thereby, in refrigeration cycle,, obviously improve as the effect that suppresses the formation of viscous substance in the kapillary in part.Finished the present invention based on above-mentioned discovery.
Put it briefly, the present invention relates to: (1) refrigeration oil, it has at 25 ℃ and is not less than 1 * 10 13The volume resistance of Ω .cm, it contains: (a) ester group oil and (b) compound of formula (1) expression:
R 1O (EO) m(PO) nR 2(1) R wherein 1It is alkyl with 1-36 carbon atom; R 2Be hydrogen atom, contain the alkyl of 1-36 carbon atom or contain the acyl group of 1-24 carbon atom; EO is the ethylene oxide group; PO is the propylene oxide group; With m be the number of 0-50 and the number that n is 0-50, its condition is m and n's and for 1-100, wherein based on 100 weight parts (a), amount (b) is the 2-25 weight part; (2), wherein in refrigeration oil, be 1-20% by weight by the compound concentrations of formula (1) expression at the refrigeration oil described in above-mentioned (1); (3) the refrigeration oil described in above-mentioned (1) or (2), wherein ester group oil contain by (i) 2-10 carbon atom saturated dihydroxyl-hexahydroxy-aliphatic polyhydroxy-alcohol and (ii) contain the saturated aliphatic mono or derivatives thereof preparation of the straight or branched of 2-9 carbon atom; (4) the refrigeration oil described in arbitrary above-mentioned (1)-(3), wherein ester group oil contains the saturated dihydroxyl-tetratomic aliphatic polyhydroxy-alcohol of 2-10 carbon atom by (i) and (ii) contains the straight or branched saturated aliphatic mono or derivatives thereof preparation of 5-9 carbon atom; (5) the refrigeration oil described in arbitrary above-mentioned (1)-(4), wherein R 1It is alkyl with 1-14 carbon atom; R 2Be hydrogen atom or the alkyl that contains 1-14 carbon atom; (6) the refrigeration oil described in arbitrary above-mentioned (1) one (5), wherein based on 100 weight parts (a), amount (b) is the 2-5 weight part; (7) be used for the working fluid composition of refrigerating machine, it contains refrigeration oil and one or more hydrogen fluorohydrocarbons that above-mentioned (1)-(6) define in any one; (8) suppress the method that viscous substance forms in refrigeration cycle, it comprises the refrigeration oil that uses above-mentioned (1)-(6) to define in any one; (9) be used to suppress the reagent that viscous substance forms in refrigeration cycle, it contains the compound of the formula (1) as active ingredient:
R 1O (EO) m(PO) nR 2(1) R wherein 1It is alkyl with 1-36 carbon atom; R 2Be hydrogen atom, contain the alkyl of 1-36 carbon atom or contain the acyl group of 1-24 carbon atom; EO is the ethylene oxide group; PO is the propylene oxide group; With m be that number and the n of 0-50 is the 0-50 number, its condition is m and n's and be 1-100.Implement best mode 1-1. ether compound of the present invention
Being used for ether compound of the present invention can be the compound of formula (1) expression:
R 1O (EO) m(PO) nR 2(1) R wherein 1It is alkyl with 1-36 carbon atom; R 2Be hydrogen atom, contain the alkyl of 1-36 carbon atom or contain the acyl group of 1-24 carbon atom; EO is the ethylene oxide group; PO is the propylene oxide group; With m be the number of 0-50 and the number that n is 0-50, its condition is m and n's and for 1-100.
The compatible ability of consideration and hydrogen fluorohydrocarbon, R 1Be to have 1-36 carbon atom, preferred 1-24 carbon atom, more preferably 1-18 carbon atom, the most preferably alkyl of 1-14 carbon atom.The compatible ability of consideration and hydrogen fluorohydrocarbon, R 2Be hydrogen atom, contain the alkyl of 1-36 carbon atom or contain the acyl group of 1-24 carbon atom; Preferred R 2Be hydrogen atom, a 1-24 carbon atom, more preferably 1-18 carbon atom, the most preferably alkyl of 1-14 carbon atom.R 2Acyl group preferably contain 1-18 carbon atom, more preferably 1-14 carbon atom.
Equally, consider electrical insulation property, thermostability, cryogenic flow kinetic force and water absorbability, m is the number of 0-50, preferred 0-30, more preferably 0-20, the most preferably number of 0-10.Consider electrical insulation property and thermostability, n is the number of 0-50, preferred 0-30, more preferably 0-20, the most preferably number of 0-10.Equally, consider the inhibition that electrical insulation property, thermostability, water absorbability and viscous substance form, m and n sum are 1-100, preferred 1-60, more preferably 1-40, also preferred 2-40, most preferably 2-30.Equally, consider and the compatible ability of hydrogen fluorohydrocarbon that ester cpds preferably has and is no more than 25 ℃, more preferably no more than 15 ℃, also preferably is no more than 0 ℃, more will preferably be no more than-15 ℃, is most preferably not exceeding-25 ℃ fusing point.Equally, consider compatible ability and water absorbability with the hydrogen fluorohydrocarbon, ester cpds has and preferably is no more than 3000, more preferably no more than 2000, also preferably is no more than 1500, is most preferably not exceeding 1000 molecular weight.
Equally, consider electrical insulation property, be used for the compound by formula (1) expression of the present invention have 25 ℃ be not less than 1 * 10 10Ω .cm preferably is not less than 1 * 10 11Ω .cm more preferably is not less than 1 * 10 12Ω .cm most preferably is not less than 1 * 10 13The volume resistance of Ω .cm conforms with hope.
The acid number that is used for the compound by formula (1) expression of the present invention there is not particular restriction.Considering to suppress Corrosion of Metallic Materials, wear resistance decline, thermostability decline and electrical insulating property descends, compound by formula (1) expression has the 1mg of being no more than KOH/g, preferably be no more than 0.2mgKOH/g, more preferably no more than 0.1mg KOH/g, the acid number that is most preferably not exceeding 0.05mg KOH/g conforms with hope.
Hydroxyl value to the compound that is used for formula of the present invention (1) expression is not specifically limited.The hydroxyl value of the compound of formula (1) expression is 0.1-500mg KOH/g, preferred 0.1-300mgKOH/g, and more preferably 0.1-250mg KOH/g, most preferably 0.1-200mg KOH/g conforms with hope.Consider wear resistance, the compound with the hydroxyl value that is not less than 0.1mg KOH/g conforms with hope, considers water absorbability, and the compound with the hydroxyl value that is no more than 500mg KOH/g conforms with hope.
Conform with and it is desirable for the compound that is used for formula of the present invention (1) expression and have low two phase separation temperatures with the hydrogen fluorohydrocarbon at low temperatures, preferably be no more than 10 ℃, more preferably no more than 0 ℃, also preferably be no more than-10 ℃, also will preferably be no more than-30 ℃, be most preferably not exceeding-50 ℃.Equally, conform with and it is desirable for the compound that is used for formula of the present invention (1) expression and at high temperature have high two phase separation temperatures with the hydrogen fluorohydrocarbon, preferably be not less than 30 ℃, more preferably be not less than 40 ℃, also preferably be not less than 50 ℃, also to preferably be not less than 60 ℃, most preferably be not less than 80 ℃.
The compound that is used for formula of the present invention (1) expression there is not special restriction 100 ℃ dynamic viscosity.Consider and the compatible ability and the wetting property of hydrogen fluorohydrocarbon that the dynamic viscosity of compound under 100 ℃ that conforms with the formula of it is desirable for (1) expression is 1-100mm 2/ s, preferred 1-50mm 2/ s, more preferably 1-30mm 2/ s, most preferably 1-20mm 2/ s.1-2. base oil (1) ester group oil
Do not have special restriction to being used for ester group oil of the present invention, as long as ester and hydrogen fluorohydrocarbon have compatible ability, pour point is no more than 0 ℃ and dissolve the compound that contains one or more oxyalkylene groups and get final product.The specific examples of ester is to be selected from following compound as preferred embodiment.(a) contain the ester that the saturated aliphatic mono or derivatives thereof of the aliphatic polyhydroxy-alcohol of saturated dihydroxyl-hexahydroxy-of 2-10 carbon atom and the straight or branched that (component-2) contains 2-9 carbon atom prepares by (component-1); (b) contain the ester that the saturated aliphatic single hydroxyl alcohol of straight or branched of 1-10 carbon atom and dicarboxylic acid-hexacarboxylic acid or derivatives thereof that (component-4) contains 2-10 carbon atom prepare by (component-3); (c) contain the ester that the mixing acid of the radical of saturated aliphatic dicarboxylic acid or derivatives thereof of the straight or branched that the aliphatic polyhydroxy-alcohol of saturated dihydroxyl-hexahydroxy-of 2-10 carbon atom and straight or branched saturated aliphatic mono or derivatives thereof that (component-2) contains 2-9 carbon atom and (component-5) contain 2-10 carbon atom prepares by (component-1); (d) contain the aliphatic polyhydroxy-alcohol of saturated dihydroxyl-hexahydroxy-of 2-10 carbon atom and the straight or branched that (component-3) contains 1-10 carbon atom by (component-1), the alcohol mixture of radical of saturated aliphatic single hydroxyl alcohol and (component-4) contain the ester that the dicarboxylic acid of 2-10 carbon atom prepares to the hexacarboxylic acid or derivatives thereof; Component-1
The alcohol that is used for component-1 is dihydroxyl-hexavalent alcohol, preferred dihydroxyl-tetrahydroxy alcohol.Consider to obtain suitable viscosity, dihydroxyl or above polyhydroxy-alcohol are preferred, consider that to avoid obtaining too high viscosity and to provide with the compatible ability of hydrogen fluorohydrocarbon hexahydroxy-or following polyhydroxy-alcohol are preferred.Equally, alcohol contains 2-10 carbon atom, preferred 2-6 carbon atom.For obtaining suitable viscosity, alcohol preferably contains 2 or above carbon atom, considers for avoiding obtaining too high viscosity and providing with the compatible ability of hydrogen fluorohydrocarbon, and alcohol preferably contains 10 or following carbon atom.Equally, consider thermotolerance, the alcohol that is used for component-1 does not contain any unsaturated link(age) and conforms with hope.
The specific examples that is used for the alcohol of component-1 comprises hindered alcohols, for example neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP), seasons four amylalcohol, two TriMethylolPropane(TMP)s and two seasons four amylalcohol; And polyhydroxy-alcohol, for example ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol, glycerine, Glycerol dimer, triglycerin, Sorbitol Powder and mannitol.Wherein, consider thermotolerance, hindered alcohols is especially preferred.Component-2
The monocarboxylic acid that is used for component-2 contains 2-9 carbon atom, preferred 5-9 carbon atom.Consider to suppress the formation of viscous substance, carboxylic acid preferably contains 2 or above carbon atom, considers and the compatible ability of hydrogen fluorohydrocarbon that carboxylic acid preferably contains 9 or following carbon atom.Consider and compatible ability, hydrolytic resistance and the thermostability of hydrogen fluorohydrocarbon that compare with the straight chain saturated aliphatic mono, the side chain saturated aliphatic carboxylic acid is preferred.On the other hand, consider oilness, compare with the side chain saturated aliphatic mono, the straight chain saturated aliphatic mono is preferred.The monocarboxylic acid that is used for component-2 in the present invention is according to refrigeration oil and the application choice that is used for the working fluid composition of refrigerating machine.Equally, consider thermostability, wish that more the monocarboxylic acid that does not conform to unsaturated link(age) is used for component-2.
The example that has that is used for the monocarboxylic acid of component-2 comprises valeric acid, isovaleric acid, 2-Methyl Butyric Acid, caproic acid, enanthic acid, 2-ethyl valeric acid, 2 methyl caproic acid, sad, 2 ethyl hexanoic acid, n-nonanoic acid, 3,5,5 Trimethylhexanoic acid etc.Equally, the specific examples of derivative that is used for the monocarboxylic acid of component-2 comprises the lower alkyl esters of monocarboxylic acid, and its alkyl contains 1-4 carbon atom, for example the acid anhydrides of monocarboxylic acid methyl esters and monocarboxylic acid ethyl ester and monocarboxylic acid.Component-3
The single hydroxyl alcohol that is used for component-3 contains 1-10 carbon atom, preferred 5-9 carbon atom.Consider and the compatible ability of hydrogen fluorohydrocarbon that alcohol preferably contains 10 or following carbon atom.Consider and the compatible ability and the hydrolytic resistance of hydrogen fluorohydrocarbon that compare with the straight chain saturated alcohol, the side chain saturated alcohol is preferred.Consider oilness, compare that straight chain radical of saturated aliphatic alcohol is preferred with the side chain saturated alcohol.The single hydroxyl alcohol that is used for component-3 in the present invention is according to refrigeration oil and the application choice that is used for the working fluid composition of refrigerating machine.Equally, consider thermostability, wish that more the single hydroxyl alcohol that does not contain unsaturated link(age) is used for component-3.
The specific examples that is used for the single hydroxyl alcohol of component-3 comprises methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, amylalcohol, 2-methyl butanol, 3-methyl butanol, 2,2-dimethyl propyl alcohol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, 2,3-dimethyl butyrate alcohol, enanthol, 2-methyl-n-amyl carbinol, 3-methyl-n-amyl carbinol, 5-methyl-n-amyl carbinol, octanol, 2-Ethylhexyl Alcohol, nonyl alcohol, 3,5,5-trimethyl hexanol, decyl alcohol, 2,4,6-trimethylammonium enanthol etc.Wherein, consider industrial availability, preferred hexanol, 3-methyl-n-amyl carbinol, enanthol, 2-Ethylhexyl Alcohol, octanol, 3,5,5-trimethyl hexanol and nonyl alcohol.Component-4
The carboxylic acid that is used for component-4 is dicarboxylic acid-hexacarboxylic acid, preferred dicarboxylic-tetracarboxylic acid, more preferably dicarboxylic acid-tricarboxylic acid.Consider to obtain suitable viscosity, dicarboxylic acid or above poly carboxylic acid are preferred, and for avoiding obtaining too high viscosity and compatible ability with the hydrogen fluorohydrocarbon is provided, hexacarboxylic acid or following poly carboxylic acid are preferred.Equally, carboxylic acid contains preferred 2-10, more preferably 4-9 carbon atom.For obtaining the compatible ability with the hydrogen fluorohydrocarbon, carboxylic acid preferably contains 10 or following carbon atom.
The specific examples that is used for the carboxylic acid of component-4 comprises the radical of saturated aliphatic dicarboxylic acid, for example succsinic acid, pentanedioic acid, hexanodioic acid, nonane diacid and sebacic acid; The radical of saturated aliphatic tricarboxylic acid, for example 1,2,3-tricarballylic acid and Beta-methyl tricarboxylic acid; And aromatic polycarboxylic acids, for example phthalic acid, terephthalic acid, benzenetricarboxylic acid and pyromellitic acid.Equally, the specific examples of derivative that is used for the carboxylic acid of component-4 comprises the lower alkyl esters of carboxylic acid, and its alkyl contains 1-4 carbon atom, for example acid anhydrides of carboxylate methyl ester and carboxylic acid, ethyl ester and carboxylic acid.Wherein consider industrial acquired, preferred pentanedioic acid and hexanodioic acid.Component-5
The dicarboxylic acid that is used for component-5 contains 2-10 carbon atom, preferred 4-6 carbon atom.Consider and the compatible ability of hydrogen fluorohydrocarbon that dicarboxylic acid preferably contains 10 or following carbon atom, same, consider thermostability, wish that the dicarboxylic acid that is used for component-5 does not contain any unsaturated link(age).
The specific examples that is used for the dicarboxylic acid of component-5 comprises the straight or branched radical of saturated aliphatic dicarboxylic acid that the above-mentioned poly carboxylic acid that is used for component-4 is listed.The specific examples of derivative that is used for the dicarboxylic acid of component-5 comprises the lower alkyl esters of dicarboxylic acid, and its alkyl contains 1-4 carbon atom, for example acid anhydrides of dicarboxylic acid methyl esters and ethyl dicarboxylate and dicarboxylic acid.
In above-mentioned (a)-(d), be used for ester of the present invention, consider and the balance of the required character of compatible ability, thermostability, oilness and the electrical insulation property of hydrogen fluorohydrocarbon that (a) ester in is especially preferred.In the ester in (a), one or more dihydroxyl-hexahydroxy-hindered alcohols that contain 2-10 carbon atom are especially preferred as polyhydroxy-alcohol and one or more saturated aliphatic mono that contains 5-9 carbon atom as the hindered ester that monocarboxylic acid prepares.
Polyhydroxy-alcohol comprise dimethyltrimethylene glycol, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, two TriMethylolPropane(TMP)s, two seasons four amylalcohol etc.The specific examples of monocarboxylic acid comprises valeric acid, isovaleric acid, 2-Methyl Butyric Acid, caproic acid, enanthic acid, 2-ethyl valeric acid, 2 methyl caproic acid, sad, 2 ethyl hexanoic acid, n-nonanoic acid, 3,5,5 Trimethylhexanoic acid etc.
The specific examples of the preferred ester (a) comprises neopentyl glycol and 3,5, the ester of 5-tri-methyl hexanoic acid preparation, the ester of dimethyltrimethylene glycol and 2 ethyl hexanoic acid preparation, TriMethylolPropane(TMP) and 3,5, the ester of 5-tri-methyl hexanoic acid preparation, TriMethylolPropane(TMP) and 2 methyl caproic acid, 2-ethyl valeric acid and 3,5, the ester of the mixing acid preparation of 5-tri-methyl hexanoic acid, TriMethylolPropane(TMP) and 2 methyl caproic acid, 2-ethyl valeric acid, 2 ethyl hexanoic acid and 3,5, the ester of the mixing acid preparation of 5-tri-methyl hexanoic acid, the ester of TriMethylolPropane(TMP) and 2 ethyl hexanoic acid preparation, TriMethylolPropane(TMP) and 2 methyl caproic acid, the ester of the mixing acid preparation of 2-ethyl valeric acid and 2 ethyl hexanoic acid, tetramethylolmethane and valeric acid and 3,5, the ester of the mixing acid preparation of 5-tri-methyl hexanoic acid, tetramethylolmethane and valeric acid, isovaleric acid and 3,5, the ester of the mixing acid preparation of 5-tri-methyl hexanoic acid, tetramethylolmethane and enanthic acid and 3,5, the ester of the mixing acid preparation of 5-tri-methyl hexanoic acid, tetramethylolmethane and 2 ethyl hexanoic acid and 3,5, the ester of the mixing acid preparation of 5-tri-methyl hexanoic acid, tetramethylolmethane and 2 methyl caproic acid, the ester of the mixing acid preparation of 2-ethyl valeric acid and 2 ethyl hexanoic acid, tetramethylolmethane and sad and 3,5, the ester of the mixing acid preparation of 5-tri-methyl hexanoic acid, tetramethylolmethane and 2 methyl caproic acid, 2-ethyl valeric acid, 2 ethyl hexanoic acid and 3,5, the ester of the mixing acid preparation of 5-tri-methyl hexanoic acid, the ester of tetramethylolmethane and 2 ethyl hexanoic acid preparation etc.
Be used for ester of the present invention and can use every kind of above-mentioned component preparation by conventional known esterification and transesterification.
In other words, the ester in above-mentioned (a)-(d) can use following component preparation by the known esterification and the transesterification of routine: ester (a): (component-1) one or more pure and mild (component-2) one or more carboxylic acids and the preparation of its derivative; Ester (b): (component-3) one or more pure and mild (component-4) one or more carboxylic acids and the preparation of its derivative; Ester (c): mixed carboxylic acid's preparation of (component-1) one or more pure and mild (component-2) one or more carboxylic acids and its derivative and (component-5) one or more carboxylic acids and its derivative; Ester (d): one or more carboxylic acid or derivatives thereof preparations of (component-1) one or more pure and mild (component-3) one or more pure alcohol mixtures and (component-4).
The acid number that is used for the above-mentioned ester that obtains of the present invention there is not particular restriction.Considering to suppress Corrosion of Metallic Materials, wear resistance decline, thermostability decline and electrical insulating property descends, ester has the 1mg of being no more than KOH/g, preferably be no more than 0.2mg KOH/g, more preferably no more than 0.1mgKOH/g, the acid number that is most preferably not exceeding 0.05mg KOH/g conforms with hope.
The hydroxyl value that is used for ester of the present invention is not specifically limited.The hydroxyl value of ester is 0.1-50mg KOH/g, preferred 0.1-30mg KOH/g, and more preferably 0.1-20mg KOH/g, most preferably 0.1-10mg KOH/g conforms with hope.Consider wear resistance, the ester with the hydroxyl value that is not less than 0.1mgKOH/g conforms with hope, considers water absorbability, and the ester with the hydroxyl value that is no more than 50mgKOH/g conforms with hope.
The iodine number (Ig/100g) that is used for ester of the present invention is not had particular restriction, consider the thermo-oxidative stability of the refrigeration oil obtain, ester preferably has and is no more than 10, more preferably no more than 5, also preferably is no more than 3, is most preferably not exceeding 1 iodine number.
Conform with it is desirable for and be used for ester of the present invention and have low two phase separation temperatures with the hydrogen fluorohydrocarbon at low temperatures, preferably be no more than 10 ℃,, also preferably be no more than-10 ℃ more preferably no more than 0 ℃, also will preferably be no more than-30 ℃, be most preferably not exceeding-50 ℃.Equally, conform with it is desirable for and be used for ester of the present invention and at high temperature have high two phase separation temperatures, preferably be not less than 30 ℃, more preferably be not less than 40 ℃, also preferably be not less than 50 ℃, also will preferably be not less than 60 ℃, most preferably be not less than 80 ℃ with the hydrogen fluorohydrocarbon.
There is not special restriction to being used for ester of the present invention 40 ℃ dynamic viscosity.Consider compatible ability and wetting property with the hydrogen fluorohydrocarbon, conform with that to it is desirable for the dynamic viscosity of ester under 40 ℃ be 1-200mm 2/ s, preferred 1-150mm 2/ s, more preferably 5-100mm 2/ s, most preferably 5-75mm 2/ s.There is not special restriction to being used for ester of the present invention 100 ℃ dynamic viscosity.Same compatible ability and the wetting property of considering with the hydrogen fluorohydrocarbon conforms with that to it is desirable for the dynamic viscosity of ester under 100 ℃ be 1-100mm 2/ s, preferred 1-50mm 2/ s, more preferably 1-30mm 2/ s, most preferably 1-15mm 2/ s.(2) mixing oil
Being used for ester group oil of the present invention also can contain its amount and can not influence mineral oil and synthetic oil with the compatible ability of hydrogen fluorohydrocarbon, for example poly-alpha olefins, alkylbenzene, the ester except that the invention described above is specifically described, polyalkylene glycol, carbonic ether, PFPE and phosphoric acid ester except that the compound that formula (1) is represented.The specific examples of synthetic oil is described in " New Edition of PhysicalChemistry of Lubrication " (Saiwai Shobo publishes, 1978) 180-224 page or leaf.1-3. the amount of the compound of ester group oil and formula (1) expression
Consider to suppress the formation of viscous substance, the amount that conforms with the ester group oil of hope and the compound that formula (1) is represented is as follows.The amount of the compound of ester group oil and formula (1) expression makes the compound concentrations of formula (1) expression be not less than micelle-forming concentration, with make this quantity enough greatly with satisfactory performance in this character of oil base that obtains freezing, comprise dynamic viscosity, volume resistance, with the compatible ability of hydrogen fluorohydrocarbon etc.Consider to suppress the formation and the volume resistance of viscous substance, based on 100 weight part ester group oil, the compound of formula (1) expression is preferably the 2-25 weight part, more preferably 2-20 weight part, also preferred 2-15 weight part, also preferred 2-12 weight part, also preferred 2-10 weight part, most preferably 2-5 weight part.
Equally, be preferably 1-20% by weight, more preferably 1-15% by weight, preferred 1-10% by weight also, most preferably 1-5% by weight in the compound concentrations of the oily Chinese style of refrigeration (1) expression.1-4. additive optionally
Be used for refrigeration oil of the present invention and also can contain conventional selective additives, for example epoxy compounds, acetal or ketal compound, carbodiimide compound, every kind all is used to remove used water or acid; With antioxidant, extreme pressure additive, oiliness activator, defoamer, detergent dispersant, sanitas, non-emulsifying agent, viscous modulus activator, metal inactivator, be used to reagent that suppresses pour point etc.1-5. refrigeration oil properties
Consider electrical insulation property, refrigeration oil of the present invention preferably is not less than 1 * 10 at 25 ℃ volume resistance 13Ω .cm.For practical application, refrigeration oil preferably is not less than 1 * 10 at 25 ℃ volume resistance 13Ω .cm leaks to suppress a large amount of electric currents.The measurement in being set at 25 ℃ thermostatted (making) of the method for volume resistance of the present invention by JISC2101 by Nagano ScienceCorporation.In above-mentioned measuring method, be used for the electrode member " ELECTRODE (model) OBE-2 " (making) and the ohmer " R8340A " (making) of liquid by Advantest by Soken Electric Corporation.2. the working fluid composition 2-1. hydrogen fluorohydrocarbon (HFC) that is used for refrigerating machine
Be not specifically limited being used for hydrogen fluorohydrocarbon of the present invention (HFC), as long as they are used to be configured for the material of the working fluid composition of refrigerating machine routinely.Their preferred embodiment comprises methylene fluoride (HFC32), 1,1-C2H4F2 C2H4F2 (HFC152a), 1,1,1-Halothane (HFC143a), 1,1,1,2-Tetrafluoroethane (HFC134a), 1,1,2,2-Tetrafluoroethane (HFC134), pentafluoride ethane (HFC125) etc., especially preferred methylene fluoride, pentafluoride ethane, 1,1,1,2-Tetrafluoroethane and 1,1, the 1-Halothane.These hydrogen fluorohydrocarbons can use separately or two or more are used in combination.
When the working fluid composition that is used for refrigerating machine therein is used for refrigerator, especially preferably use 1,1,2,2-Tetrafluoroethane (HFC134a).When the working fluid composition that is used for refrigerating machine therein is used for air conditioning machinery and industrial refrigeration machinery, consider refrigerating efficiency, the preferred hydrogen fluorohydrocarbon that contains methylene fluoride (HFC32) that uses.More preferably can use methylene fluoride, pentafluoride ethane and 1,1,1, the mixture of the mixture of 2-Tetrafluoroethane, methylene fluoride and pentafluoride ethane or methylene fluoride and 1,1,1, the mixture of 2-Tetrafluoroethane.The preferred example of hydrogen fluorohydrocarbon, although be not subjected to the restriction of components by weight percent ratio, comprise and contain by weight 23% methylene fluoride, 25% pentafluoride ethane and by weight 52%1 by weight, 1,1,2-Tetrafluoroethane or hydrogen fluorohydrocarbon contain the methylene fluoride of 40-60% by weight and the pentafluoride ethane of 60-40% by weight; Or the hydrogen fluorohydrocarbon contains 20-40% methylene fluoride and 80-60%1 by weight by weight, 1,1, and the 2-Tetrafluoroethane.2-2. hydrogen fluorohydrocarbon (HFC) and the oily blending ratio of refrigeration
At the working fluid composition that is used for refrigerating machine of the present invention that contains hydrogen fluorohydrocarbon (HFC), the oily blending ratio with the hydrogen fluorohydrocarbon of freezing there is not particular restriction.Refrigeration oil is 1 with the preferred blending ratio of hydrogen fluorohydrocarbon: 50-20: 1 (weight ratio), more preferably 1: 10-5: 1 (weight ratio).Consider to obtain enough refrigeration capacities, refrigeration oil and the part by weight of hydrogen fluorohydrocarbon make preferably and freeze oily and the part by weight of hydrogen fluorohydrocarbon is to compare at 20: 1 that the hydrogen fluorohydrocarbon is present in the composition with larger proportion.Considering to be used for the preferred viscosities of the working fluid composition of refrigerating machine, is to compare at 1: 50 with the refrigeration oil and the part by weight of hydrogen fluorohydrocarbon, and refrigeration is oily to be present in the composition with larger proportion.3. suppress viscous substance method that forms and the reagent that is used to suppress viscous substance formation
Is a kind of of following compound by the oil that freezes of the present invention with the viscous substance that the working fluid composition that is used for refrigerating machine suppresses to form: the 1) compound that owing to heating, empty G﹠W the oil deterioration that freezes is formed in refrigeration cycle.2) the processing chemical substance of in the production of refrigerating machine and assembling process, using, the oil of for example drawing, cutting liquid, cosmoline, press oil and cleaning liquor.3) compound that in refrigeration cycle, makes these chemical process materials go bad and form owing to heating, empty G﹠W.
In the present invention, contain the refrigeration oil of the compound of above-mentioned formula (1) expression by use, in refrigeration cycle, for example viscous substance can obviously suppress in kapillary.Therefore, the present invention can be provided at and suppress the method that viscous substance forms in the refrigeration cycle, it is characterized in that using refrigeration oil of the present invention.In addition, the invention provides and suppress the reagent that viscous substance forms in refrigeration cycle, it contains the compound of formula (1) expression as activeconstituents.
The present invention describes in more detail by following processing and implementation example, and described embodiment is not used in and limits the scope of the invention.
The compound and the viscous substance of ester group oil, formula (1) expression that is used for the processing and implementation example is as follows.Ester group oil 1
The ester of the mixing acid preparation of tetramethylolmethane (1.0mol) and 2 ethyl hexanoic acid (1.96mol) and 3,5,5 Trimethylhexanoic acid (2.07mol)
At 40 ℃ dynamic viscosities (hereinafter referred is " Vis40 "): 70.2mm 2/ s.
At 100 ℃ dynamic viscosities (hereinafter referred is " Vis100 "): 8.63mm 2/ s.
Acid number: 0.01mg KOH/g.
Hydroxyl value: 2.4mg KOH/g.
Iodine number: be no more than 1.0Ig/100g.Ester group oil 2
The ester of tetramethylolmethane (1.0mol) and 3,5,5 Trimethylhexanoic acid (3.0mol) preparation
Vis40：50.19mm 2/s。
Vis100：7.14mm 2/s。
Acid number: be lower than 0.01mg KOH/g.
Hydroxyl value: 0.8mg KOH/g.
Iodine number: be no more than 1.0Ig/100g.The compd A of formula (1) expression: MeO (PO) 24(EO) 6HB:MeO (PO) 24(EO) 6MeC:C 4O (EO/PO=1.6/1.6) H, EO/PO is a random copolymers, wherein C 4It is the straight chain butyl.D:C 12O (EO) 6(PO) 2H, wherein C 12It is the straight chain dodecyl.E:C 12O (PO) 2(EO) 6H, wherein C 12It is the straight chain dodecyl.F:C 12O (EO/PO=5/2) H, EO/PO is a random copolymers, wherein C 12It is the straight chain dodecyl.G:C 13O (PO) 5(EO) 8H, wherein C 13It is the side chain tridecyl.H:C 13O (PO) 7(EO) 11H, wherein C 13It is the side chain tridecyl.
In above-claimed cpd, Me is a methyl, and EO is ethylene oxide group and PO propylene oxide group.Equally, the mol ratio of ethylene oxide group and propylene oxide group is the numerical value of average group compound in above-claimed cpd.Viscous substance A: polybutylene-based synthetic metalworking fluid;
Vis40：300mm 2/s。Viscous substance B: mineral oil based metalworking fluid;
Vis40：20mm 2/s。
Viscous substance C: the degradation production of viscous substance A.
Among the present invention, products of metamorphism is by dividing use heating tube test set " HT-201 " (being made by Komatsu Setsubi) heating viscous substance A preparation in the airflow that provides under 270 ℃ of temperature with 8ml/.Embodiment 1
For estimating the inhibition ability of viscous substance that the present invention is used for the working fluid composition of refrigerating machine, test the dissolving power of viscous substance by the following method at the working fluid composition that is used for refrigerating machine.
Specifically, the test set of the compatible ability of use and hydrogen fluorohydrocarbon is with 1,1,1, and 2-Tetrafluoroethane (HFC134a) and the oil of being tested mix with part by weight at 95: 5, determine that by general inspection the temperature range of hydrogen fluorohydrocarbon uniform dissolution is at 0-60 ℃.Obviously, weight ratio and temperature condition are set at inlet capillaceous, and this place is the easiest adhesion the in the refrigerating machine operation.
Based on 100 weight part ester groups oil 1 or 2, add a certain amount of compd A, B, C, D, E, F, G or H of formula (1) expression in table 1 or 2 of being shown in here, with preparation refrigeration oil.1 weight part viscous substance A is mixed the oil of being tested with preparation with 100 weight parts refrigeration oil.In addition, the refrigeration oil of measuring preparation is at 25 ℃ volume resistance, the measurement in being set at 25 ℃ thermostatted (being made by Nagano ScienceCorporation) of the method for volume resistance by JISC2101.In above-mentioned measuring method, be used for the electrode member " ELECTRODE (model) OBE-2 " (making) and the ohmer " R8340A " (making) of liquid by Advantest by Soken Electric Corporation.The results are shown in table 1 and 2.Table 1
Viscous substance
Product compound (weight part) temperature range 11 A 10 3.8 * 10 of amount * (Ω .cm) uniform dissolution of working fluid composition volume resistance dissolving power invention ester group oil formula (1) of oil are used to freeze 13Be not less than 40 ℃ of 21 B 25 1.2 * 10 13Be not less than 30 ℃ of 31 B 20 2.2 * 10 13Be not less than 30 ℃ of 41 B 15 3.1 * 10 13Be not less than 40 ℃ of 51 B 10 4.0 * 10 13Be not less than 40 ℃ of 61 B 5 6.6 * 10 13Be not less than 50 ℃ of 71 C 2 2.0 * 10 13Be not less than 40 ℃ of 81 D 5 3.8 * 10 1360 ℃ of 91 E 20 1.6 * 10 13Be not less than 50 ℃ of 10 1 E 15 2.1 * 10 13Be not less than 50 ℃ of 11 1 E 10 1.9 * 10 13Be not less than 50 ℃ of 12 1 E 5 5.0 * 10 1360 ℃ of 13 1 F 5 3.7 * 10 13Be not less than 50 ℃ of 14 2 B 5 1.8 * 10 13Be not less than 40 ℃ of 15 2 C 5 1.2 * 10 13Be not less than 40 ℃ of 16 2 E 5 2.5 * 10 13Be not less than 20 ℃ of 17 2 G 5 3.1 * 10 13Be not less than 50 ℃ of 18 2 H 5 2.2 * 10 13Be not less than 50 ℃ of *: based on the amount of the ester group oil of 100 weight parts.Table 2
Viscous substance
Relatively product compound (weight part) temperature range 1 1-0 2.1 * 10 of amount * (Ω .cm) uniform dissolution of ester group oil formula (1) of oily working fluid composition volume resistance dissolving power is used to freeze 15Do not dissolve 21 B 1 8.4 * 10 at 60 ℃ 13Do not dissolve 31 B 27 9.1 * 10 at 60 ℃ 12Be not less than 30 ℃ of 41 B 30 7.8 * 10 12Be not less than 30 ℃ of 51 E 1 7.9 * 10 13Do not dissolve 61 E 27 8.8 * 10 at 60 ℃ 12Be not less than 40 ℃ of 71 E 30 5.7 * 10 12Be not less than 40 ℃ of 81 F 1 8.5 * 10 13Do not dissolve 91 F 30 7.1 * 10 at 60 ℃ 12Be not less than 30 ℃ 10 2-0 5.0 * 10 1460 ℃ of 11 2 E 1 4.0 * 10 1360 ℃ of 12 2 E 30 1.3 * 10 12Be not less than 20 ℃ of 13 2 H 1 3.6 * 10 1360 ℃ of 14 2 H 30 1.4 * 10 12Be not less than 50 ℃ of *: based on the amount of the ester group oil of 100 weight parts.
As shown in table 1 and 2, to add under the situation of compd A-H with the amount that is no less than 2 weight parts respectively, to compare with independent ester group oil 1 or 2 based on 100 weight part ester groups oil 1 or 2, the temperature of uniform dissolution obviously reduces.Therefore, when can be observed the effect that suppresses viscous substance with 2 weight parts or compd A-H of more measuring adding formula (1) expression respectively.On the other hand, when when adding the compd A of formula (1) expression-H with the amount that surpasses 25 weight parts respectively based on 100 weight part ester groups oil 1 or 2, volume resistance is lower than 1 * 10 13(Ω .cm), therefore, based on the ester group oil of 100 weight parts, the preferred amount of the compound of formula (1) expression is the 2-25 weight part.Embodiment 2
In 100 weight part ester group oil 1, add the compd B of 11.11 weight part formulas (1) expression or the Compound C preparation refrigeration oil of 2.04 weight part formulas (1) expression.In the refrigeration oil that 100 weight parts obtain, add the oil that 5 weight part viscous substance B are used to test with preparation.
The oil seals of every kind of test of 210 grams in 200W reciprocation compressor capillaceous is housed, are encapsulated into 70 grams 1,1,1, and 2-Tetrafluoroethane (HFC134a), machine are operate continuously 200 hours under 110 ℃ the condition in the temperature at the top of reciprocation compressor.After operation in 200 hours, the viscous substance by on the visual control method observation kapillary the results are shown in the table 3.
Compare with the compound comparison product 15 that does not wherein comprise formula (1) expression, product of the present invention shows obvious a spot of viscous substance on kapillary.
Table 3
(200W reciprocation compressor, viscous substance B)
Formula (1) expression amount * forms on kapillary
Viscous substance invention product 19 1 B 11.11 no invention product 20 1 C 2.04 of the compound of ester group oil (weight part) incomparably than product 15 1--have a *: based on the quantity of the ester group oil of 100 weight parts.Embodiment 3
The Compound C preparation refrigeration oil that in 100 weight part ester group oil 2, adds the expression of 2.04 weight part formulas (1).In the refrigeration oil that 100 weight parts obtain, add the oil that 5 weight part viscous substance A are used to test with preparation.
Restrain the oil seal of every kind of test in 150W reciprocation compressor capillaceous is housed with 310, be encapsulated into 100 grams 1,1,1 then, 2-Tetrafluoroethane (HFC134a), machine are operate continuously 200 hours under 110 ℃ the condition in the temperature at the top of reciprocation compressor.After operation in 200 hours, the viscous substance by on the visual control method observation kapillary the results are shown in the table 4.
Compare with the compound comparison product 16 that does not wherein comprise formula (1) expression, product of the present invention shows obvious a spot of viscous substance on kapillary.
Table 4
(150W reciprocation compressor, viscous substance A)
Formula (1) expression quantity * shape on kapillary
Viscous substance invention product 21 2 C 2.04 that the compound of ester group oil (weight part) becomes incomparably than product 16 2--have a *: based on the quantity of the ester group oil of 100 weight parts.Embodiment 4
The compd B preparation refrigeration oil that in 100 weight part ester group oil 2, adds the expression of 11.11 weight part formulas (1).In the refrigeration oil that 100 weight parts obtain, add the oil that 5 weight part viscous substance B are used to test with preparation.
The oil seals of every kind of test of 310 grams in 1kw rotary compressor capillaceous is housed, are encapsulated into 380 grams 1,1,1, and 2-Tetrafluoroethane (HFC134a), machine are operate continuously 200 hours under 110 ℃ the condition in the temperature at the top of rotary compressor.After operation in 200 hours, the viscous substance by on the visual control method observation kapillary the results are shown in the table 5.
Compare with the compound comparison product 17 that does not wherein comprise formula (1) expression, product of the present invention shows obvious a spot of viscous substance on kapillary.
Table 5
(1kW rotary compressor, viscous substance B)
Formula (1) expression amount * shape on kapillary
Viscous substance invention product 22 2 B 11.11 that the compound of ester group oil (weight part) becomes incomparably than product 17 2--have a *: based on the amount of the ester group oil of 100 weight parts.Embodiment 5
The Compound C preparation refrigeration oil that in 100 weight part ester group oil 1, adds the expression of 2.04 weight part formulas (1).In the refrigeration oil that 100 weight parts obtain, add the oil that 5 weight part viscous substance C are used to test with preparation.
The oil seals of every kind of test of 210 grams in 200W reciprocation compressor capillaceous is housed, are encapsulated into 70 grams 1,1,1 then, and 2-Tetrafluoroethane (HFC134a), machine are operate continuously 200 hours under 110 ℃ the condition in the temperature at the top of reciprocation compressor.After operation in 200 hours, the viscous substance by on the visual control method observation kapillary the results are shown in the table 6.
Compare with the compound comparison product 18 that does not wherein comprise formula (1) expression, product of the present invention shows obvious a spot of viscous substance on kapillary.
Table 6
(200W reciprocation compressor, viscous substance C)
Formula (1) expression amount * shape on kapillary
Viscous substance invention product 23 1 C 2.04 that the compound of ester group oil (weight part) becomes incomparably than product 18 1--have a *: based on the amount of the ester group oil of 100 weight parts.
Commercial Application
According to the present invention, owing to add special ether compound in ester group oil, the refrigeration that obtains oil and the working fluid composition that is used for refrigeration machine show that the formation of obviously good capillary or cycle period stickum suppresses.
Described the present invention, but obviously can change in every way. This variation does not relate to runs counter to the spirit and scope of the present invention, and all these change is significantly for a person skilled in the art, is included in the scope of following claims.

Claims (9)

1. one kind has at 25 ℃ and to be not less than 1 * 10 13The refrigeration oil of the volume resistance of Ω .cm, it contains:
(a) ester group oil and
(b) compound of formula (1) expression:
R 1O (EO) m(PO) nR 2(1) R wherein 1It is alkyl with 1-36 carbon atom; R 2Be hydrogen atom, contain the alkyl of 1-36 carbon atom or contain the acyl group of 1-24 carbon atom; EO is the ethylene oxide group; PO is the propylene oxide group; With m be the number of 0-50 and the number that n is 0-50, its condition is m and n's and for 1-100, wherein based on 100 weight parts (a), amount (b) is the 2-25 weight part.
2. the refrigeration oil of claim 1 wherein is 1-20% by weight in the compound concentrations of the oily Chinese style of refrigeration (1) expression.
3. claim 1 or 2 refrigeration oil, wherein ester group oil contain by (i) 2-10 carbon atom saturated dihydroxyl-hexahydroxy-aliphatic polyhydroxy-alcohol and (ii) contain the saturated aliphatic mono or derivatives thereof preparation of the straight or branched of 2-9 carbon atom.
4. the refrigeration oil of claim 1-3 described in each, wherein ester group oil contains the saturated dihydroxyl-tetratomic aliphatic polyhydroxy-alcohol of 2-10 carbon atom by (i) and (ii) contains the saturated aliphatic mono or derivatives thereof preparation of the straight or branched of 5-9 carbon atom.
5. the refrigeration oil of claim 1-4 described in each, wherein R 1It is alkyl with 1-14 carbon atom; R 2Be hydrogen atom or the alkyl that contains 1-14 carbon atom.
6. the refrigeration oil of claim 1-5 described in each, wherein based on 100 weight parts described (a), the amount of described (b) is the 2-5 weight part.
7. working fluid composition that is used for refrigerating machine, it contains refrigeration oil and one or more hydrogen fluorohydrocarbons of each definition among the claim 1-6.
8. one kind is suppressed the method that viscous substance forms in refrigeration cycle, and it comprises the refrigeration oil that uses each definition among the aforesaid right requirement 1-6.
9. one kind is used to suppress the reagent that viscous substance forms in refrigeration cycle, and it contains the compound of the formula (1) as active ingredient:
R 1O (EO) m(PO) nR 2(1) R wherein 1It is alkyl with 1-36 carbon atom; R 2Be hydrogen atom, contain the alkyl of 1-36 carbon atom or contain the acyl group of 1-24 carbon atom; EO is the ethylene oxide group; PO is the propylene oxide group; With m be the number of 0-50 and the number that n is 0-50, its condition is m and n's and for 1-100.
CN97180544A 1996-12-11 1997-12-03 Refrigeration oil and working fluid composition for refrigerating machine Pending CN1239983A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP352134/96 1996-12-11
JP8352134A JPH10168479A (en) 1996-12-11 1996-12-11 Refrigerator oil and refrigerator working fluid composition

Publications (1)

Publication Number Publication Date
CN1239983A true CN1239983A (en) 1999-12-29

Family

ID=18422012

Family Applications (1)

Application Number Title Priority Date Filing Date
CN97180544A Pending CN1239983A (en) 1996-12-11 1997-12-03 Refrigeration oil and working fluid composition for refrigerating machine

Country Status (6)

Country Link
EP (1) EP0944688B1 (en)
JP (1) JPH10168479A (en)
KR (1) KR20000057459A (en)
CN (1) CN1239983A (en)
DE (1) DE69708320T2 (en)
WO (1) WO1998026024A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408938A (en) * 2011-10-11 2012-04-11 中国石油化工股份有限公司 Refrigerating machine oil composition and preparation method thereof
CN101024793B (en) * 2006-02-23 2013-04-17 株式会社日本能源 Refrigerating machine oil for hydrocarbon refrigerant and refrigerating machine system using the same
CN103509631A (en) * 2013-04-16 2014-01-15 广东美芝制冷设备有限公司 Compressor, and refrigeration plant provided with compressor
CN112430454A (en) * 2019-08-26 2021-03-02 丰田自动车株式会社 Cooling liquid composition and cooling system

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4092780B2 (en) * 1997-10-17 2008-05-28 ダイキン工業株式会社 Refrigeration and air conditioning equipment
JP4885339B2 (en) * 1998-05-13 2012-02-29 出光興産株式会社 Refrigerator oil composition
JP2002194368A (en) * 2000-10-17 2002-07-10 Nippon Mitsubishi Oil Corp Freezer oil
WO2005012467A1 (en) * 2003-08-01 2005-02-10 Nippon Oil Corporation Refrigerating machine oil compositions
WO2005012469A1 (en) 2003-08-01 2005-02-10 Nippon Oil Corporation Refrigerating machine oil composition
JP5407157B2 (en) 2008-03-18 2014-02-05 ダイキン工業株式会社 Refrigeration equipment
WO2012173878A1 (en) * 2011-06-14 2012-12-20 Dow Global Technologies Llc Natural and synthetic ester-containing lubricants having enhanced hydrolytic stability
EP2909886A4 (en) 2012-10-19 2016-06-15 Univ North Carolina Ion conducting polymers and polymer blends for alkali metal ion batteries
US9755273B2 (en) 2013-04-01 2017-09-05 The University Of North Carolina At Chapel Hill Ion conducting fluoropolymer carbonates for alkali metal ion batteries
JP6224965B2 (en) * 2013-09-12 2017-11-01 出光興産株式会社 Mixing composition for refrigerator
JP2015140994A (en) * 2014-01-30 2015-08-03 日立アプライアンス株式会社 Air conditioner, and refrigerator oil
JP6394333B2 (en) * 2014-12-02 2018-09-26 Ａｇｃ株式会社 Lubricating oil composition and refrigerator system
US10077231B2 (en) 2015-02-03 2018-09-18 Blue Current, Inc. Functionalized fluoropolymers and electrolyte compositions
JP2017057278A (en) * 2015-09-16 2017-03-23 出光興産株式会社 Refrigerator oil, composition for refrigerator and compressive refrigerator

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6050396B2 (en) * 1980-06-26 1985-11-08 三洋化成工業株式会社 Base oils and compositions for metal lubrication
JPS5838793A (en) * 1981-08-31 1983-03-07 Sanyo Chem Ind Ltd Lubricating oil composition
JPH0532985A (en) * 1991-07-26 1993-02-09 Kyoseki Seihin Gijutsu Kenkyusho:Kk Refrigerating machine oil composition
ATE209242T1 (en) * 1991-10-11 2001-12-15 Ici Plc WORKING FLUIDS
JPH06100881A (en) * 1992-09-18 1994-04-12 Kyoseki Seihin Gijutsu Kenkyusho:Kk Refrigerator oil composition
JPH0873880A (en) * 1994-09-09 1996-03-19 Idemitsu Kosan Co Ltd Refrigerator oil composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101024793B (en) * 2006-02-23 2013-04-17 株式会社日本能源 Refrigerating machine oil for hydrocarbon refrigerant and refrigerating machine system using the same
CN102408938A (en) * 2011-10-11 2012-04-11 中国石油化工股份有限公司 Refrigerating machine oil composition and preparation method thereof
CN102408938B (en) * 2011-10-11 2014-10-15 中国石油化工股份有限公司 Refrigerating machine oil composition and preparation method thereof
CN103509631A (en) * 2013-04-16 2014-01-15 广东美芝制冷设备有限公司 Compressor, and refrigeration plant provided with compressor
CN112430454A (en) * 2019-08-26 2021-03-02 丰田自动车株式会社 Cooling liquid composition and cooling system
CN112430454B (en) * 2019-08-26 2022-08-19 丰田自动车株式会社 Cooling liquid composition and cooling system

Also Published As

Publication number Publication date
KR20000057459A (en) 2000-09-15
EP0944688B1 (en) 2001-11-14
JPH10168479A (en) 1998-06-23
DE69708320D1 (en) 2001-12-20
EP0944688A1 (en) 1999-09-29
WO1998026024A1 (en) 1998-06-18
DE69708320T2 (en) 2002-07-11

Similar Documents

Publication Publication Date Title
CN1239983A (en) Refrigeration oil and working fluid composition for refrigerating machine
JP2967574B2 (en) Refrigeration equipment
CN1119587C (en) Refrigerator
CN1288228C (en) Lubricating oil compound for freezer
KR102463654B1 (en) Tetrafluoropropene-based azeotrope composition
FR3061906A1 (en) COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE
EP3571260A1 (en) Composition comprising 2,3,3,3-tetrafluoropropene
CN1433457A (en) Refrigerating machine oil composition for carbon dioxide refrigerant
CN1097088C (en) Lubricant composition for refrigerating machine employing HFC-32, HFC-125 or HFC-134a
CN1494583A (en) Refrigerator lubricant compositions
CN1190429A (en) Refrigerating machine oil and lubricating method adopting same
KR100266957B1 (en) Lubricating oil additive, lubricating oil and working fluid for refrigerators
WO2014034568A1 (en) Lubricant composition
KR20140050052A (en) Low gwp heat transfer compositions containing difluoromethane, a fluorinated ethane and 1,3,3,3-tetrafluoropropene
WO2018220127A1 (en) Trifluoroethylene-based compositions and uses thereof
CN1068901C (en) Refrigerating machine oil composition and refrigeration and compressor using refrigerating machine oil composition
CN1782042A (en) Lubricating oil composition of freezer
FR3064264A1 (en) COMPOSITION BASED ON TETRAFLUOROPROPENE
JP4278749B2 (en) Refrigerating machine oil composition and lubrication method using the composition
EP0913457A2 (en) Low viscosity energy efficient polyol-ester containing refrigerant
CN1031758C (en) Lubricant for refrigeration compressors
US20200040243A1 (en) Quasi-azeotropic composition comprising 2,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene
JPH1112585A (en) Refrigerating machine oil and composition for refrigerating machine-operating fluid
JP5149714B2 (en) Refrigerator oil composition
CN117365902A (en) Compressor and refrigerating device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication